JP5154005B2 - Methacrylate as stabilizer for polymer polyols - Google Patents

Abstract

This invention relates to ethylenically unsaturated macromers which contain reactive unsaturation, and to a process for preparing these ethylenicallly unsaturated macromers which contain reactive unsaturation. The process of preparing these ethylenically unsaturated macromers comprises reacting a monofunctional compound which corresponds to a specific formula with at least one alkylene oxide, in the presence of at least one alkoxylation catalyst. The ethylenically unsaturated macromers correspond to the formula set forth herein. This invention also relates to preformed stabilizers comprising ethylenically unsaturated macromers, to a process for preparing these preformed stabilizers, to polymer polyols comprising these preformed stabilizers, and to a process of preparing these polymer polyols which comprise these preformed stabilizers. Polymer polyols comprising ethylenically unsaturated macromers and a process for their preparation are also described.

Description

  The present invention relates to methacrylate-based macromers corresponding to specific structures useful for forming preformed stabilizers that can be used to produce polymer polyols. Furthermore, the present invention provides a process for preparing methacrylate-based macromers useful for stabilizing polymer polyols, novel preformed stabilizers comprising these macromers, these preforms comprising these novel macromers. Method for producing foamed stabilizer, method for producing polymer polyol comprising novel preformed stabilizer, polymer polyol comprising these novel preformed stabilizers, polymer polyol comprising ethylenically unsaturated macromer And a polymer polyol comprising these novel ethylenically unsaturated macromers.

  Polymer polyols, also known as filled polyols, are sticky liquids comprising fine granules dispersed in a polyol. Examples of solids used are styrene-acrylonitrile copolymers and polyureas. The solid is typically produced by in situ polymerization of monomers in a base polyol. Polymer polyols are usually used in the production of polyurethane foam.

  As used herein, a macromer is defined as a molecule comprising one or more polymerizable double bonds and one or more hydroxyl-terminated polyether tails. Various macromers are known and have previously been used to stabilize polymer polyols by copolymerization with one or more ethylenically unsaturated monomers such as styrene and acrylonitrile. Because of the similarity in chemical composition, the polyether tail is energetically advantageous for association with polyol molecules in the continuous phase, rather than association with styrene-acrylonitrile copolymers. The polyether tail extends into the continuous phase, thereby forming a “brush” layer near the particle liquid interface that shields van der Waals attraction between particles. This phenomenon is known as steric stabilization. In order to form a brush layer that effectively shields Van der Waals forces, several conditions must be met. The polyether tail needs to be similar in chemical composition to the continuous phase so that it extends completely into the continuous phase and is not adsorbed by the particles. Also, the surface coverage and molecular weight need to be sufficiently high so that the interfacial brush layer is of sufficient thickness to avoid agglomeration of solid particles.

  Many methods are known in the art for introducing reactive unsaturation into polyols, thereby forming macromers. US Pat. No. 6,013,731 is a reaction of a polyol with an unsaturated isocyanate (eg, isocyanatoethyl methacrylate (IEM) or α, α-dimethylmetaisopropenylbenzyl isocyanate (ie, TMI)) or more Several techniques are taught, including the reaction of a polyol with maleic acid or maleic anhydride, followed by isomerization of the maleate bond to a sex fumarate bond. Macromers produced by transesterification of vinylalkoxysilanes and polyols are disclosed in European Patent EP 0,162,589 (Patent Document 2).

  The term preformed stabilizer refers to a macromer containing reactive unsaturation (eg, acrylate, methacrylate, maleate, etc.), a monomer (ie, acrylonitrile, styrene, methyl methacrylate, etc.), and optionally a diluent or Obtained by reacting in a solvent (ie methanol, isopropanol, toluene, ethylbenzene, polyether polyol, etc.) to obtain a copolymer (eg a dispersion with low solids (eg <20%) or soluble grafts etc.) Defined as an intermediate.

  Preformed stabilizers (PFS) are particularly useful for producing polymer polyols having low viscosity at high solids. In the preformed stabilizer process, the macromer reacts with the monomer to form a copolymer composed of the macromer and the monomer. These copolymers comprising macromers and monomers are usually referred to as preformed stabilizers (PFS). The reaction conditions can be controlled so that the copolymer moiety precipitates out of solution and forms a solid. In many applications, dispersions with low solids (eg, 3-15% by weight) are obtained. Preferably, the reaction conditions are controlled such that the particle size is small, thereby allowing the particles to act as a “seed” in the polymer polyol reaction.

  For example, US Pat. No. 5,196,476 (Patent Document 3) polymerizes a macromer with one or more ethylenically unsaturated monomers in the presence of a free radical polymerization initiator and a liquid diluent in which the preformed stabilizer is essentially insoluble. A preformed stabilizer composition produced by making the composition is disclosed. European patent EP 0,786,480 describes that in the presence of a free radical initiator, 5 to 40% by weight of one or more ethylenically unsaturated monomers, at least 30% by weight (which may contain induced unsaturation) ( Disclosed is a process for preparing a preformed stabilizer by polymerizing in the presence of a liquid polyol comprising a coupled polyol (based on the total weight of the polyol). These preformed stabilizers are stable and can be used to produce polymer polyols having a narrow particle size distribution. Coupled polyols are necessary to achieve small particle sizes (preferably in the range of 0.1-0.7 microns) in preformed stabilizers. US Pat. Nos. 6,013,731 and 5,990,185 also describe a preformed stable comprising a reaction product of a polyol, a macromer, at least one ethylenically unsaturated monomer, and a free radical polymerization initiator. An agent composition is disclosed.

Less material, since it can be used to sterically stabilize the particles, large, bulky molecules are known to be effective macromers. For example, see European Patent EP 0,786,480 (Patent Document 4). Generally speaking, this is due to the fact that highly branched polymers require a much less branched polymer because they have a much larger excluded volume than linear molecules (eg monools). to cause. US Pat. No. 5,196,476 discloses that two or more functionalities, preferably three or more functionalities, are suitable for producing macromers. European patents EP 0,162,589 and US Pat. No. 5,990,185 describe macromers and their use to produce polymer polyols. Here, the macromer is produced by transesterification of a vinylalkoxysilane and a polyol. Suitable macromers comprise the reaction product of vinyltrimethoxysilane, vinyltriethoxysilane, or vinyltripropoxysilane and a mixture of a group of polyether polyols characterized by a functionality in the range of 2-6. . Such a macromer would be expected to have at least three polyether tails. Also, coupling of polyfunctional polyols with polyisocyanates is known and described in the field of polymer polyols as a suitable means for increasing the molecular weight of macromers. European Patent EP 0,786,480 (Patent Document 4) discloses a method for producing a preformed stabilizer. Here, the liquid polyol comprises at least 30% of a coupled polyol. As described therein, a high concentration of coupled polyols is useful in preformed stabilizers (PFS) to obtain particles having a small particle size. And the introduction of reactive unsaturation into the coupled polyol is a useful means for incorporating the coupled polyol into the particles. US Pat. No. 6,013,731 discloses that dispersion stability can be significantly enhanced by coupling high molecular weight polyols to form higher molecular weight products. Macromers made from polyols with low intrinsic unsaturation (<0.020 meq / gram) are also described in US Pat. No. 6,013,731. Further, the 731 patent shows that such polyols have a low concentration of oxyalkylated, allylic unsaturation-containing monols, and therefore the high concentration of monools present in conventional polyols Is advantageous because it reduces the average functionality of

  Macromers based on multifunctional polyols having multiple sites of reactive unsaturation are described in US Pat. No. 5,196,476. As described therein, there is an upper limit on the concentration of unsaturation when producing the macromer with the maleic anhydride route. If the molar ratio of unsaturation per mole of polyol is too high, it is likely that species having one or more double bonds per molecule will be formed. Typically, the 476 patent contains from about 0.5 to about 1.5 moles, preferably from about 0.7 to about 1.1 moles of reactive inertness for each mole of alkoxylated polyol adduct. Use saturated compounds.

  There are also examples in the field of macromers based on “Zerol”. As used herein, zerol is a polyether that does not have a terminal primary hydroxyl group. There are a series of patents issued to Dow Chemical relating to the production of zerol by derivatizing polyether monools with adducts containing reactive unsaturation. US Patent 4,394,491 (Patent Document 6), 4,477,603 (Patent Document 7), 4,493,908 (Patent Document 8), 4,500,675 (Patent Document 9), 4,663,475 (Patent Document 10), 4,513,124 (Patent Document 11), 4,588,830 (Patent Document 12) And 4,640,935. These patents describe that they use semi-batch methods without preformed stabilizers, that they focus primarily on acrylate / methacrylate unsaturation, and final production when monools are used The product is similar in that it is a zerol that has no free hydroxyl groups. The key to each patent is the way in which monool derivatization is performed.

US Pat. No. 5,854,386 discloses stabilizers for polymer polyols containing both hydroxyl and unsaturated functionalities. These are prepared by oxyalkylating an unsaturated monomer having at least one oxyalkylatable hydrogen in the presence of an effective amount of a DMC catalyst and optionally in the presence of a free radical polymerization inhibitor. Is done. These stabilizers are preferably of two formulas: R [— (— R ² —O—) _n H] _o or R — (— X — {— (R ² —O) _n —H} _m ) _o [Wherein o is an integer between 1 and 8; n is an integer such that the average value is a product n · o of 10 to 500; R ² is alkylene or substituted alkylene] Yes; X is a linking group; and R contains at least one site of ethylenic or ethylenic (acetylenic) unsaturation, may be substituted with a non-reactive group, and optionally It is a C _2-30 hydrocarbon containing interspersed heteroatoms] and corresponds to a mixture containing one or more of the above. R can be aliphatic, cycloaliphatic, aromatic, arylaliphatic, heteroaromatic, etc. (provided that when R is aromatic or heteroaromatic, the aromatic ring structure is at least one ethylenic or Substituted with an ethylenic group-containing group).

US Pat. No. 4,680,358 describes a polyether macromer having a styryl functional head group at one end and a terminal hydroxyl group at the other end. These macromers are polymerizable through a head group having a copolymerizable monomer (for example, acrylonitrile, styrene, acrylic acid, etc.) and a terminal hydroxyl group at the other end. This polymerization of the macromer yields a polymacromer, i.e., a graft or comb copolymer, having a saturated hydrocarbon backbone with polyether branches. These macromers are formed by cationic ring-opening polymerization of cyclic ethers in conjunction with alkenyl alcohols.
US Patent 6,013,731 European patent EP 0,162,589 US Patent 5,196,476 European patent EP 0,786,480 US Patent 5,990,185 US Patent 4,394,491 US Patent 4,477,603 US Patent 4,493,908 US Patent 4,500,675 US Patent 4,663,475 US Patent 4,513,124 US Patent 4,588,830 US Patent 4,640,935 US Patent 5,854,386 US Patent 4,680,358

  The present invention comprises a methacrylate-based macromer corresponding to a particular structure, a process for producing the macromer, and the macromer useful for forming preformed stabilizers that can be used to produce polymer polyols. Novel preformed stabilizer, method for producing the preformed stabilizer, method for producing polymer polyol comprising the preformed stabilizer, polymer polyol comprising the preformed stabilizer, ethylenically unsaturated An object is to provide a method for producing a polymer polyol comprising a macromer, and a polymer polyol comprising the ethylenically unsaturated macromer.

  The present invention relates to novel macromers comprising at least one polyether chain terminated with one or more ethylenically unsaturated double bonds and hydroxyl groups, production of these novel macromers, polymer polyols comprising said novel macromers, and The preparation of these polymer polyols from these novel macromers is described. The novel macromers of the present invention have at least one polyether chain with at least one double bond and a terminal hydroxy group per molecule. A key advantage of the present invention is the ability to produce low viscosity polymer polyols using a variety of macromers based on novel α, β-unsaturated carbonyl compounds.

  That is, the present invention relates to ethylenically unsaturated macromers, methods for producing these ethylenically unsaturated macromers, preformed stabilizers based on ethylenically unsaturated macromers, methods for producing these preformed stabilizers, these The present invention relates to a polymer polyol comprising a preformed stabilizer (ie, a stable dispersion), and a method for producing these polymer polyols (ie, a stable dispersion). The present invention also relates to polymer polyols produced from ethylenically unsaturated macromers and methods for producing these polymer polyols.

  The method for producing the novel ethylenically unsaturated macromer of the present invention comprises:

（１）（ａ）式：

(1) (a) Formula:

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) reacting in the presence of at least one catalyst.

The present invention also provides:
(A) Formula:

〔式中、
Ｒは、水素原子、１〜８個の炭素原子を含有する分枝または直鎖の炭化水素基、または６〜１２個の炭素原子を含有するアリール基を示し、
Ｒ”は、水素原子、１〜８個の炭素原子を含有し、飽和または不飽和であり得る、分枝または直鎖の炭化水素基、または６〜１２個の炭素原子を含有するアリール基を示し、
Ａは、塩素原子、臭素原子、フッ素原子、ヨウ素原子、またはＯＲ’基（式中、Ｒ’は、水素原子または１〜８個の炭素原子を有するアルキル基を示す。）を示す。〕
に対応する化合物を、
（ｂ）ＯＨ価１０〜３００および官能価２〜１５を有するポリエーテルポリオールと、
必要に応じて、
（ｃ）少なくとも一つの触媒
の存在下、反応させた生成物を含んでなる、新規エチレン性不飽和マクロマーに関する。

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) It relates to a novel ethylenically unsaturated macromer comprising the product reacted in the presence of at least one catalyst.

The present invention also provides:
(1) (A) the ethylenically unsaturated macromer;
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
Further, the present invention relates to a method for producing a preformed stabilizer, which includes free radical polymerization in the presence of a chain transfer agent (E) as necessary.

These preformed stabilizers are another aspect of the present invention. This preformed stabilizer
(A) the ethylenically unsaturated macromer;
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
And (E) a free radical polymerized product in the presence of a chain transfer agent, if necessary.

Furthermore, the present invention also relates to polymer polyols comprising these preformed stabilizers and methods for their production.
This method for producing a polymer polyol comprises (1) (I) a base polyol, (II) the preformed stabilizer, (III) at least one ethylenically unsaturated monomer, and (IV) at least one free radical. Free radical polymerization in the presence of a polymerization initiator and, optionally, (V) a chain transfer agent.

  These polymer polyols of the present invention comprise (I) a base polyol, (II) the preformed stabilizer, (III) at least one ethylenically unsaturated monomer, and (IV) at least one free radical polymerization initiation. And, optionally, (V) a product obtained by free radical polymerization in the presence of a chain transfer agent.

The present invention also relates to polymer polyols comprising ethylenically unsaturated macromers and methods for producing these polymer polyols.
These polymer polyols are
(I) a base polyol;
(II) the ethylenically unsaturated macromer,
(A) Formula:

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
And A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) an ethylenically unsaturated macromer comprising a product reacted in the presence of at least one catalyst;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
It comprises a free radical polymerized product.

  The process for producing these polymer polyols comprises (A) (I) a base polyol, (II) the ethylenically unsaturated macromer, (III) at least one ethylenically unsaturated monomer, and (IV) at least one free monomer. Free radical polymerization in the presence of a radical polymerization initiator and, if necessary, (V) a chain transfer agent. Suitable ethylenically unsaturated macromers for this process are those described above for polymer polyols made directly from ethylenically unsaturated macromers.

  Another aspect of the invention relates to foams made from these polymer polyols and methods for making these foams. These foams comprise the reaction product of a polyisocyanate or prepolymer thereof and an isocyanate-reactive component. Here, at least one of the polymer polyols is used as at least part of the isocyanate-reactive component. Suitable polymer polyols for foams and methods for making the foams include polymer polyols made directly from ethylenically unsaturated macromers, and preforms based on ethylenically unsaturated macromers, as described herein And polymer polyols produced from a stabilizer.

As the ethylenically unsaturated macromer of the present invention,
(A) Formula:

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
And A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom or an OR ′ group (R ′ represents a hydrogen atom or an alkyl group containing 1 to 8 carbon atoms). ]
A compound corresponding to
(B) compounds comprising a product reacted with one or more polyether polyols having an OH number of about 10 to about 300 and a functionality of about 2 to about 15.

In the above formula for compound (a):
R represents hydrogen, methyl, ethyl, propyl or butyl;
R ″ represents a hydrogen, methyl, ethyl, propyl, butyl, phenyl, or alkylene group (eg, ethenyl or propenyl), and A represents a chlorine, bromine, iodine, or OR ′ group wherein R ′ is Represents hydrogen, methyl or ethyl].

  Suitable compounds used as component (a) in the ethylenically unsaturated macromer include, for example, acryloyl chloride, acryloyl bromide, methacryloyl chloride, methacryloyl bromide, acrylic acid, methacrylic acid, methyl methacrylate, cinnamic acid, Examples thereof include compounds such as methyl cinnamate, 2,4-hexadienoic acid, and methyl sorbate. More preferably, it is an acrylate compound. Most preferred is methacrylate.

  In the ethylenically unsaturated macromer, suitable polyether polyols for component (b) that react with compound (a) have a functionality of at least about 2, preferably at least about 3, and more preferably at least about 4. Things. The functionality of suitable polyether polyols is about 15 or less, preferably about 10 or less, and most preferably about 8 or less. Also suitable polyether polyols can have a functionality in the range (including upper and lower limits) between any combination of these upper and lower limits. Suitable polyether polyols have an OH number of at least about 10, preferably at least about 15, and most preferably at least about 18. Polyether polyols also typically have an OH number of about 300 or less, preferably about 200 or less, and most preferably about 100 or less. Suitable polyether polyols may also have an OH number in the range (including upper and lower limits) between any combination of these upper and lower limits. Suitable polyether polyols have (number average) molecular weights typically greater than about 400, preferably at least about 2,000, and most preferably at least about 4,000. The polyether polyol typically has a (number average) molecular weight of 15,000 or less, more preferably 12,000 or less, and most preferably 9,000 or less. Also suitable polyether polyols can have a (number average) molecular weight in the range (including upper and lower limits) between any combination of these upper and lower limits.

  These polyether polyols also have a functionality in the range of about 2 to about 15, preferably about 3 to about 10, and most preferably about 4 to about 8; about 10 to 300, preferably about 15 From about 18 to about 100; and more than 400 to about 15,000, preferably from about 2,000 to 12,000, and most preferably about 4 May have a (number average) molecular weight in the range of 1,000 to 9,000.

  Examples of such compounds include polyoxyethylene glycol, triol, tetrol and higher functional polyols, polyoxypropylene glycol, triol, tetrol and higher functional polyols, mixtures thereof, and the like. . When used as a mixture, ethylene oxide and propylene oxide can be added simultaneously or sequentially to provide an internal block, end block or random distribution of oxyethylene and / or oxypropylene groups in the polyether polyol. Suitable starters or initiators for these compounds include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine, and the like. Is mentioned. A suitable polyether polyol for the base polyol component can be formed by alkoxylation of the starter.

  Other base polyols suitable for the present invention include alkylene oxide adducts of non-reducing sugars and sugar derivatives, alkylene oxide adducts of phosphoric acid and polyphosphorus acid, alkylene oxide adducts of polyphenols, Examples include polyols produced from natural oils (such as castor oil), and alkylene oxide adducts of polyhydroxyalkanes other than those described above.

  Exemplary polyhydroxyalkane alkylene oxide adducts include, for example, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5- and 1 , 6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6- and 1,8-dihydroxyoctane, 1,10-dihydroxydecane, glycerol, 1,2,4-trihydroxy Alkylene such as butane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, caprolactan, polycaprolactone, xylitol, arabitol, sorbitol, mannitol And oxide adducts.

  Other polyols that can be used include alkylene oxide adducts of non-reducing sugars, where the alkoxide has 2 to 4 carbon atoms. Non-reducing sugars and sugar derivatives include sucrose, alkyl glycosides (eg, methyl glycoside, ethyl glycoside, etc.), glycol glycosides (eg, ethylene glycol glycoside, propylene glycol glycoside, glycerol glycoside, 1,2,6-hexanetriol glycoside) Etc.), as well as alkylene oxide adducts of alkyl glycosides as disclosed in US Pat. No. 3,073,788, the disclosure of which is incorporated herein by reference.

  Other suitable polyols include polyphenols and preferably the alkylene oxide adducts thereof, where the alkylene oxide has 2 to 4 carbon atoms. Suitable polyphenols include, for example, bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, novolac resins, condensation products of various phenolic compounds and acrolein (1,1,3-tris ( Hydroxyphenyl) propane), condensation products of various phenolic compounds and glyoxal, glutaraldehyde, other dialdehydes (including 1,1,2,2-tetrakis (hydroxyphenol) ethane), and the like.

  Also, alkylene oxide adducts of phosphoric acid and polyphosphoric acid are useful polyols. These include ethylene oxide, 1,2-epoxy-propane, epoxybutane, 3-chloro-1,2-epoxypropane and the like as suitable alkylene oxides. Phosphoric acid, phosphoric acid, polyphosphoric acid (eg, tripolyphosphoric acid, polymetaphosphoric acid, etc.) are desirable for use in the present invention.

  The reaction between the compound corresponding to formula (a) and the polyether polyol (b) can be carried out in the presence of one or more catalysts (c). Virtually any catalyst known to be suitable for esterification and / or transesterification can be used as component (c) in the present invention. Examples of catalysts (c) suitable for the present invention include, for example, acetic acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, tetrabutyl titanate, tetraethyl titanate, potassium acetate, sodium hydroxide, triethylamine. , Tributylamine, pyridine, and N, N-dimethylaniline.

  In the process for preparing the ethylenically unsaturated macromer, the compound corresponding to formula (a) is typically optionally at a temperature of about 25 ° C. to about 250 ° C. for about 1 hour to about 10 hours. It reacts with the polyether polyol (b) in the presence of a catalyst. This reaction is suitably at a temperature of about 60 ° C. to about 200 ° C. for a period of about 2 hours to about 7 hours.

  According to the method for producing a preformed stabilizer, the ethylenically unsaturated macromer is at least in the presence of at least one free radical polymerization initiator, and optionally a liquid diluent, and optionally a chain transfer agent. Free radical polymerization with one ethylenically unsaturated monomer.

In the preformed stabilizer and the process for producing the preformed stabilizer, the ethylenically unsaturated macromer can be used. The ethylenically unsaturated macromer for this aspect of the invention is
(A) Formula:

[Wherein R, R ″ and A have the same meanings as described above.]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) comprising the product reacted in the presence of at least one catalyst.

With respect to the preformed stabilizers of the present invention and methods for their production, (a) in the compounds corresponding to the above formulas used to produce the ethylenically unsaturated macromers,
R represents hydrogen, methyl or ethyl;
R ″ represents hydrogen, methyl, ethyl or phenyl;
And A preferably represents chloride, hydroxyl, methoxy or ethoxy.

Further, (a) in a compound corresponding to the above formula,
R represents hydrogen or methyl;
R ″ represents hydrogen or phenyl;
And A particularly preferably represent hydroxyl or methoxy.

  Suitable ethylenically unsaturated monomers for the preformed stabilizers of the present invention include, for example, aliphatic conjugated dienes (eg, butadiene and isoprene); monovinylidene aromatic monomers (eg, styrene, α-methylstyrene, (t -Butyl) styrene, chlorostyrene, cyanostyrene and bromostyrene); α, β-ethylenically unsaturated carboxylic acids and their esters (eg acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-hydroxy acrylate) Ethyl, butyl acrylate, itaconic acid, maleic anhydride, etc.); α, β-ethylenically unsaturated nitriles and amides (eg acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N-dimethylacrylamide, N- ( Dimethylaminomethyl) acrylami Vinyl esters (eg, vinyl acetate); vinyl ethers, vinyl ketones, vinyl halides and vinylidene halides, and a wide range of other ethylenically unsaturated materials that are copolymerizable with the above adduct monomers or reactive monomers. . It will also be appreciated that a mixture of two or more of the above monomers can be suitably used in the production of preformed stabilizers. Among the above monomers, monovinylidene aromatic monomers (particularly styrene) and ethylenically unsaturated nitriles (particularly acrylonitrile) are preferred.

  When using a mixture of monomers, it is preferred to use a mixture of two monomers. These monomers are typically in a weight ratio of 80:20 (styrene: acrylonitrile) to 40:60 (S: AN), and preferably 75:25 (S: AN) to 50:50 (S: AN) by weight ratio.

  Suitable free radical polymerization initiators for this aspect of the invention include, for example, peroxides, persulfates, perborates, percarbonates, azo compounds, and the like containing both alkyl and aryl hydroperoxides. Some specific examples include hydrogen peroxide, di (t-butyl) peroxide, t-butylperoxydiethyl acetate, t-butylperoctoate, t-butylperoxyisobutyrate, t-butylperoxy3.5 , 5-trimethylhexanoate, t-butylperbenzoate, t-butylperoxypivalate, t-amylperoxypivalate, t-butylperoxy-2-ethylhexanoate, lauroyl peroxide, cumene hydroperoxide, t-butyl Examples thereof include catalysts such as hydroperoxide, azobis (isobutyronitrile), 2,2′-azobis- (2-methylbutyronitrile).

  Suitable catalyst concentrations are based on the total weight of the components (ie, 100% by weight of the total weight of macromer, ethylenically unsaturated monomer, free radical polymerization initiator and optionally liquid diluent and / or chain transfer agent). From about 0.01 wt% to about 2 wt%, preferably from about 0.05 wt% to 1 wt%, and most preferably from 0.05 wt% to 0.3 wt%.

  Suitable diluents for the preformed stabilizer of the present invention include, for example, compounds such as monools (ie, monohydroxy alcohol), polyols, hydrocarbons, ethers, and mixtures thereof. Suitable monools include all alcohols containing at least one carbon atom, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec.-butanol, tert-butanol, n-pentanol, 2 -Pentanol, 3-pentanol and the like, and mixtures thereof. A preferred monool is isopropanol.

  Suitable polyols include poly (oxypropylene) glycols, triols and higher functionality polyols. Such polyols include poly (oxypropylene-oxyethylene) polyols; however, desirably the oxyethylene content should comprise less than about 50%, preferably less than about 20% of the total amount. . Ethylene oxide can be incorporated in any manner along the polymer chain. In other words, ethylene oxide can be incorporated into the inner block as a terminal block or can be randomly distributed along the polymer chain. It is well known in the art that polyols contain various amounts of underivatized unsaturation. Preferred polyols of the present invention are those produced using DMC catalysis. These polyols have low unsaturation, typically less than 0.02 meq / g, measured using ASTM D2849-69. The degree of unsaturation does not have any adverse effect on the formation of the polymer polyols of the present invention.

  For the purposes of the present invention, useful polyols should have a number average molecular weight of about 400 or greater. As used herein, the number average is a theoretical value derived from the hydroxyl number. The true number average molecular weight can be somewhat smaller depending on how much the true molecular functionality is less than the starting or theoretical functionality.

  The polyol used may have a hydroxyl number that varies widely. In general, the hydroxyl number of the polyol used in the present invention can range from about 20 or less to about 280 or more. Hydroxyl number is defined as the number of milligrams of potassium hydroxide required to fully hydrolyze a fully phthalated derivative made from 1 gram of polyol. Also the hydroxyl number is the equation:

[Where,
OH = polyol hydroxyl number;
f = functionality, ie the average number of hydroxyl groups per molecule of polyol; and m. w. = Molecular weight of polyol]
Can be defined by

  The exact polyol used will depend on the end use of the polyurethane product produced. The molecular weight of the hydroxyl number is suitably selected to give a flexible or somewhat flexible foam or elastomer when the polymer polyol made from the polyol is converted to polyurethane. The polyol preferably has a hydroxyl number of about 50 to about 150 for a somewhat flexible foam and a hydroxyl number of about 30 to about 70 for a flexible foam. Such limitations are not intended to be limiting, but are merely illustrative of the many possible combinations of the polyol co-reactants.

  Also, although not preferred, any other type of known polyol may be used. Among the polyols that can be used are one or more polyols from the following composition classes known to those skilled in the art of polyurethane chemistry: (a) alkylene oxides of non-reducing sugars and sugar derivatives Adducts; (b) alkylene oxide adducts of phosphoric acid and polyphosphoric acid; (c) alkylene oxide adducts of polyphenols; (d) polyols from natural oils (eg, castor oil); Alkylene oxide adduct of hydroxyalkane.

  Exemplary alkylene oxides of polyhydroalkanes include, among others, 1,3-dihydroxypropane, 1,3-dihydroxy-butane, 1,4-dihydroxybutane, 1,4-, 1,5- and 1,6- Dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6- and 1,8-dihydroxyoctane, 1,10-dihydroxydecane, glycerol, 1,2,4-trihydroxybutane, 1 , 2,6-trihydroxyhexane, 1,1,1-trimethylol-propane, pentaerythritol, caprolactone, polycaprolactone, xylitol, arabitol, sorbitol, mannitol and other alkylene oxide adducts.

  Another class of polyols that can be used are alkylene oxide adducts of non-reducing sugars, where the alkylene oxide has 2 to 4 carbon atoms. Among non-reducing sugars and sugar derivatives, those intended are sucrose, alkyl glycosides (eg methyl glycoside, ethyl glycoside, etc.), glycol glycosides (eg ethylene glycol glycoside, propylene glycol glycoside, glycerol glycoside, 1, 2,6-hexanetriol glycosides), as well as alkylene oxide adducts of alkyl glycosides as described in US Pat. No. 3,073,788, the disclosure of which is incorporated herein by reference.

  Furthermore, a useful class of phenols is polyphenols, preferably alkylene oxide adducts thereof, where the alkylene oxide adduct has 2 to 4 carbon atoms. Among the polyphenols, those intended are, for example, bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, novolac resins, condensation products of various phenolic compounds and acrolein (the simplest of these are 1,1,3-tris (hydroxyphenyl) propane), condensation products of various phenolic compounds with glyoxal, glutaraldehyde, and other dialdehydes (the simplest of which is 1,1,2 , 2-tetrakis (hydroxyphenol) ethane).

  The alkylene oxide adducts of phosphoric acid and polyphosphoric acid are another useful class of polyols. Ethylene oxide, 1,2-epoxypropane, epoxybutane, 3-chloro-1,2-epoxypropane and the like are suitable alkylene oxides. Phosphoric acid, phosphoric acid, polyphosphoric acid (eg, tripolyphosphoric acid, polymetaphosphoric acid, etc.) are desirable for use in this regard.

  Suitable polyol components used as diluents in the present invention typically include, for example, suitable starter materials having 4 or more hydroxyl groups (eg, pentaerythritol, sorbitol, sorbitol diether, mannitol, mannitol Diether, arabitol, diether of arabitol, sucrose, an oligomer of polyvinyl alcohol or glycidol), an alkylene oxide adduct, a mixture thereof and the like.

  When a mixture of monool and polyol is used as the diluent for the preformed stabilizer, the polyol preferably comprises only the lower amount of the diluent and the monool comprises the higher amount. In general, the polyol comprises less than 30% by weight of the diluent, preferably less than about 20% by weight, and most preferably less than about 15% by weight. The amount of polyol component present in the diluent is below the concentration at which gelation occurs in the preformed stabilizer.

  In general, the amount of diluent is> 40% by weight, based on 100% by weight of PFS (preformed stabilizer).

  Chain transfer agents may also be present in the preformed stabilizers of the present invention and in the process for producing the preformed stabilizer. Suitable chain transfer agents for this aspect of the invention include, for example, isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl-mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride. Is mentioned. The chain transfer agent is generally called a molecular weight modifier. These compounds are used in customary amounts to control the molecular weight of the copolymer.

  Suitable methods for the preparation of preformed stabilizers are, for example, U.S. Pat. 5,814,699 and 5,854,358 (the disclosures of which are incorporated herein by reference) are similar to the known methods described in US Pat. In general, the process for producing preformed stabilizers is similar to the process for producing polymer polyols. The temperature range is not critical and can be changed to about 80 ° C. to about 150 ° C. or more, preferably about 115 ° C. to about 125 ° C. The catalyst and temperature should be selected so that the catalyst has a reasonable cracking rate with respect to hold-up time in the reactor for a continuous flow reactor or feed time for a semi-batch reactor.

  The mixing conditions used in this method can be obtained by using a backside mixing reactor (eg, stirred flask or stirred autoclave). This type of reactor keeps the reaction mixture relatively homogeneous and prevents a localized high macromer to monomer ratio such as occurs in a tubular reactor where all of the monomer is added at the start of the reaction. .

  In a preferred embodiment, the preformed stabilizer of the present invention comprises a dispersion in a diluent and optional unreacted monomers. Here, preformed stabilizers are probably present as individual molecules or as micellar molecules or on the surface of small polymer particles.

  The combination of conditions selected for the production of the preformed stabilizer should not lead to cross-linking or gel formation in the preformed stabilizer that can adversely affect the critical ability in the production of the polymer polyol composition. The combination of too low diluent concentration, too high precursor and / or monomer concentration, too high catalyst concentration, too long reaction time, and too much unsaturation in the precursor can lead to ineffective preforms from crosslinking or gelling. Can produce stabilizers.

  Particularly suitable methods for preparing the preformed stabilizers of the present invention include, for example, those described in US Pat. No. 5,196,476 and US Pat. No. 6,013,731, the disclosure of which is incorporated herein by reference. It is done. Suitable diluents and relative concentrations, ethylenically unsaturated monomers and relative concentrations, free radical initiators and relative concentrations, and process conditions are described in US Pat. No. 5,196,476 and US Pat. No. 6,013,731, the disclosures of which are incorporated herein by reference. Are disclosed). Clearly, the ethylenically unsaturated macromers suitable for the present invention are different from the macromers described in these references and thus give rise to structurally different preformed stabilizers.

  The polymer polyol (ie, the stability dispersion) of the present invention comprises a base polyol, the preformed stabilizer, and one or more ethylenically unsaturated monomers linked to at least one free radical initiator and optionally. In the presence of a transfer agent, the product comprises a free radical polymerized product, and a method for producing a polymer polyol (ie, a stable dispersion) comprises free radical polymerizing these components. The resulting polymer polyol exhibits a high solids content (ie, 30-60% by weight) based on the total weight of the resulting polymer polyol. The solid content of the polymer polyol is preferably in the range of 40 to 50% by weight. These polymer polyols also exhibit low viscosity (i.e., 2000-10,000 cSt, preferably 4,000-6,000 cSt); good filterability, and are preferably white.

  Suitable base polyols for this aspect of the invention include, for example, base polyols such as polyether polyols. Suitable polyether polyols preferably include those having a functionality of at least about 2, more preferably at least about 3. The functionality of suitable polyether polyols is about 8 or less, preferably about 6 or less, and most preferably about 5 or less. Also suitable polyether polyols can have a functionality in the range (including upper and lower limits) between any combination of these upper and lower limits. Suitable polyether polyols have an OH number of at least about 10, preferably at least about 15, and most preferably at least about 20. Also, the polyether polyol typically has an OH number of about 180 or less, preferably about 100 or less, and most preferably about 70 or less. Suitable polyether polyols may also have an OH number in the range (including upper and lower limits) between any combination of these upper and lower limits. Suitable polyether polyols typically have a (number average) molecular weight of greater than about 600, preferably at least about 2,000, and most preferably at least about 3,000. The polyether polyols typically have a (number average) molecular weight of 15,000 or less, more preferably 12,000 or less, and most preferably 8,000 or less. Also suitable polyether polyols can have a (number average) molecular weight in the range (including upper and lower limits) between any combination of these upper and lower limits.

  These polyether polyols also have a functionality in the range of about 2 to about 8, preferably about 2 to about 6, and most preferably about 3 to about 5; about 10 to 180, preferably about 15 An OH number in the range of from about 100 to about 100, and most preferably from about 20 to about 70; It may have a (number average) molecular weight in the range of ~ 8,000.

  Examples of such compounds include polyoxyethylene glycol, triol, tetrol and higher functionality polyols, polyoxypropylene glycol, triol, tetrol and higher functionality polyols, mixtures thereof and the like. When used as a mixture, ethylene oxide and propylene oxide can be added simultaneously or sequentially to provide an internal block, end block or random distribution of oxyethylene and / or oxypropylene groups in the polyether polyol. Suitable starters or initiators for these compounds include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine, and the like. Is mentioned. A suitable polyether polyol for the base polyol component can be formed by alkoxylation of the starter.

  Other base polyols suitable for the present invention include alkylene oxide adducts of non-reducing sugars and sugar derivatives, alkylene oxide adducts of phosphoric acid and polyphosphoric acid, alkylene oxide adducts of polyphenols, natural oils such as castor oil ) And other alkylene oxide adducts of polyhydroxyalkanes other than those described above.

  Exemplary polyhydroxyalkane alkylene oxide adducts include, for example, 1,3-dihydroxypropane, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5- and 1 , 6-dihydroxyhexane, 1,2-, 1,3-, 1,4-, 1,6- and 1,8-dihydroxyoctane, 1,10-dihydroxydecane, glycerol, 1,2,4-trihydroxy Alkylene such as butane, 1,2,6-trihydroxyhexane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, caprolactan, polycaprolactone, xylitol, arabitol, sorbitol, mannitol And oxide adducts.

  Other polyols that can be used include alkylene oxide adducts of non-reducing sugars, where the alkoxide has 2 to 4 carbon atoms. Non-reducing sugars and sugar derivatives include sucrose, alkyl glycosides (eg, methyl glycoside, ethyl glycoside, etc.), glycol glycosides (eg, ethylene glycol glycoside, propylene glycol glycoside, glycerol glycoside, 1,2,6-hexanetriol glycoside) Etc.), as well as alkylene oxide adducts of alkyl glycosides as disclosed in US Pat. No. 3,073,788, the disclosure of which is incorporated herein by reference.

  Other suitable polyols include polyphenols and preferably the alkylene oxide adducts thereof, where the alkylene oxide has 2 to 4 carbon atoms. Suitable polyphenols include, for example, bisphenol A, bisphenol F, condensation products of phenol and formaldehyde, novolac resins, condensation products of various phenolic compounds and acrolein (1,1,3-tris ( Hydroxyphenyl) propane), condensation products of various phenolic compounds and glyoxal, glutaraldehyde, other dialdehydes (including 1,1,2,2-tetrakis (hydroxyphenol) ethane), and the like.

  Also, alkylene oxide adducts of phosphoric acid and polyphosphoric acid are useful polyols. These include ethylene oxide, 1,2-epoxy-propane, epoxybutane, 3-chloro-1,2-epoxypropane and the like as suitable alkylene oxides. Phosphoric acid, phosphoric acid, polyphosphoric acid (eg, tripolyphosphoric acid, polymetaphosphoric acid, etc.) are desirable for use in the present invention.

  Suitable preformed stabilizers for this aspect of the invention include those described above.

  Suitable ethylenically unsaturated monomers for the polymer polyols of the present invention and methods for their production include the ethylenically unsaturated monomers described above for the production of preformed stabilizers. Other suitable monomers include, for example, aliphatic conjugated dienes (eg, butadiene and isoprene); monovinylidene aromatic monomers (eg, styrene, α-methylstyrene, (t-butyl) styrene, chlorostyrene, cyanostyrene, and Bromostyrene); α, β-ethylenically unsaturated carboxylic acids and esters thereof (eg acrylic acid, methacrylic acid, methyl methacrylate, ethyl acrylate, 2-hydroxyethyl acrylate, butyl acrylate, itaconic acid, maleic anhydride) Acids, etc.); α, β-ethylenically unsaturated nitriles and amides (eg acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N, N-dimethylacrylamide, N- (dimethylaminomethyl) acrylamide etc.); vinyl esters ( For example, vinyl acetate ); Vinyl ethers, vinyl ketones, vinyl halides and vinylidene halides, and a wide range of other ethylenically unsaturated materials that are copolymerizable with the adduct monomers or reactive monomers. It will also be appreciated that a mixture of two or more of the above monomers is suitably used in the preparation of preformed stabilizers. Among the above monomers, monovinylidene aromatic monomers (particularly styrene) and ethylenically unsaturated nitriles (particularly acrylonitrile) are preferred. According to this aspect of the invention, these ethylenically unsaturated monomers preferably include styrene and its derivatives, acrylonitrile, methyl acrylate, methyl methacrylate, vinylidene chloride, and styrene and acrylonitrile are particularly preferred. Monomer.

  Styrene and acrylonitrile should be used in an amount sufficient so that the weight ratio styrene: acrylonitrile (S: AN) can be about 80:20 to 30:70, more preferably about 75:25 to 50:50. Is preferred. These ratios are appropriate for polymer polyols and their method of manufacture, regardless of whether they comprise the ethylenically unsaturated macromer or preformed stabilizer of the present invention.

  Generally, the amount of ethylenically unsaturated monomer present in the polymer polyol comprising the preformed stabilizer is at least about 30% by weight based on 100% by weight of the polymer polyol. It is preferred that the solids content is from about 35 wt% to about 70 wt%, more preferably from about 35 wt% to less than 60 wt%, and most preferably from about 40 wt% to about 50 wt%.

  Generally, the amount of ethylenically unsaturated monomer present in the polymer polyol comprising the ethylenically unsaturated macromer of the present invention is at least about 20% by weight based on 100% by weight of the polymer polyol. The solid content is preferably about 20% to about 45% by weight.

  Suitable free radical initiators include those described above for the preparation of preformed stabilizers. Among useful initiators, a half-life that is satisfactory within the temperature range used to form the stabilizer (ie, the half-life should be less than about 25% of the residence time in the reactor at a given time. And a catalyst having a certain). Suitable initiators for this part of the invention include acyl peroxides (eg, didecanoyl peroxide and dilauroyl peroxide), alkyl peroxides (eg, t-butylperoxy-2-ethylhexanoate, t-butyl peroxide). Valate, t-amyl peroctoate, 2,5-dimethyl-hexane-2,5-di-per-2-ethylhexoate, t-butyl perneodecanoate, t-butyl perbenzoate and 1,1 -Dimethyl-3-hydroxybutylperoxy-2-ethylhexanoate and azo catalysts (eg, azobis (isobutyronitrile), 2,2'-azobis- (2-methoxylbutyronitrile), and mixtures thereof Most preferred are the acyl peroxides and azo catalysts described above, and particularly preferred initiators are azobis (isobutyro Comprising a trill).

  The amount of initiator used in the present invention is not critical and can vary widely. In general, the amount of initiator ranges from about 0.01% to 2% by weight, based on 100% by weight of the final polymer polyol. Increasing catalyst concentration results in increased monomer conversion up to a specific point in time, but beyond this, further increases do not result in substantial increased conversion. The particular catalyst concentration chosen is usually an optimal value that takes into account all factors including cost.

  Suitable chain transfer agents for the present invention include, for example, isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, methylene chloride. The chain transfer agent is generally called a molecular weight modifier. These compounds are used in customary amounts to control the molecular weight of the copolymer.

  Polymer polyols comprising the preformed stabilizers of the present invention include, for example, U.S. Pat. Manufactured using methods as disclosed in 5,554,662, 5,594,066, 5,814,699 and 5,854,358, the disclosures of which are incorporated herein by reference. As described therein, a low polyol to monomer ratio is maintained throughout the reaction mixture during the process. This is achieved by using conditions that provide rapid conversion of the monomer to polymer. In practice, a low polyol to monomer ratio is maintained by controlling the temperature and mixing conditions for semi-batch and continuous operations and by slowly adding monomer to the polyol for semi-batch operations.

  The presence of (I) a base polyol, (II) an ethylenically unsaturated macromer, (III) at least one ethylenically unsaturated monomer, (IV) at least one free radical polymerization initiator and (V) a chain transfer agent. The various components of the polymer polyol of the present invention comprising the free radical polymerized product below include those described above for the polymer polyol comprising the preformed stabilizer of the present invention. Of course, these polymer polyols can be used in place of preformed stabilizers in the preformed stabilizers and in the process for making preformed stabilizers, using the ethylenically unsaturated macromer as a reactant. A polyol is formed. The remaining components, their relative amounts and / or ratios are the same as described above unless otherwise stated.

  These polymer polyols comprising one or more ethylenically unsaturated macromers corresponding to those described above for preformed stabilizers are, for example, U.S. Patents 3,875,258, 3,931,092, 3,950,317, 3,953,393, 4,014,846, 4,093,573, 4,372,005, 4,334,049. 4,454,255, 4,458,038, 4,689,354, 4,690,956, Re 29,014, 4,305,861, 5,093,412, 5,254,667, 6,172,164 and Re 33,291, and U.S. Patents 4,524,157, 4,539,340, Re 28,715 and Re 29,118 Manufactured) by utilizing the method disclosed in (incorporated).

  In particularly preferred embodiments of polymer polyols comprising ethylenically unsaturated macromers, the ethylenically unsaturated macromers described herein and in the claims are ethylenic for polymer polyols and methods for their production. It is preferred to be used as an unsaturated macromer.

  The temperature range is not critical and can vary from about 100 ° C to about 140 ° C or more. The preferred range is 115-125 ° C. As noted herein, the catalyst and temperature are such that the catalyst has a reasonable decomposition rate with respect to the hold-up time in the reactor for a continuous flow reactor or the feed time for a semi-batch reactor. Should be selected.

  The mixing conditions used in this method can be obtained by using a backside mixing reactor (eg, stirred flask or stirred autoclave). This type of reactor keeps the reaction mixture relatively homogeneous, and in certain tube reactors, such as in the first stage of a “macro” reactor, such a reactor is in the first stage. Prevents localized high polyol-to-monomer ratios such as occur when operated with all added monomers.

  Utilization of the process as described in US Pat. Nos. 5,196,476 and 6,013,731 is a polymer polyol having a wide range of monomer compositions, polymer contents and polymer polyols that cannot otherwise be produced with the required stability. This is suitable for this aspect of the present invention. However, whether to utilize the methods disclosed in US Pat. Nos. 5,916,476 and 6,013,731 is essentially such that process parameters can be produced without using any of these methods a satisfactory polymer polyol. Depends on whether or not.

  The polymer polyol of the present invention comprises a dispersion. Here, the polymer particles (which are either individual particles or aggregates of individual particles) are relatively small in size, and in a preferred embodiment substantially all are less than about 1 micron. To 3 microns. However, when a high styrene content is used, the particles tend to be large; however, the resulting polymer polyol is more highly useful, especially when the end use requires as little scorch as possible. In preferred embodiments, substantially all of the product (ie, greater than about 99%) can pass through the filter used in the filtration hindrance (filterability) test described in conjunction with the examples. This is a relatively sophisticated mechanical system currently used for mass production of polyurethane products, including those with impact type agitation that requires the use of filters that cannot tolerate any significant amount of relatively large particles. In all types it ensures that the polymer polyol product can be successfully processed. Less severe applications are satisfied when about 50% of the product passes through the filter. Some applications may also find useful products that pass only about 20% or less through the filter. Thus, the polymer polyols of the present invention desirably have a product that only 20% passes through the filter, preferably at least 50% passes through the filter, and most preferably substantially all passes through the filter. Intended.

  The filtration hindrance test provides a rigorous test of the stability of the polymer polyol. Thus, satisfactory filtration hindrance properties should certainly be preferred, but commercially available stable polymer polyols for a variety of applications have their viscosities and centrifugeable solid levels (this test is also an example) To be fully defined). Thus, polymer polyols are considered stable as long as the viscosity is about 6,000 cSt or less at 25 ° C. and the centrifugeable solids are less than about 10% (preferably less than 5%).

  According to the present invention, the stabilizer is present in an amount sufficient to ensure that satisfactory stabilization results in the desired filtration hindrance, centrifugable solids level and viscosity. In this regard, the amount of preformed stabilizer is generally in the range of about 1 wt% to about 20 wt% (preferably about 1 wt% to about 10 wt%) based on the total feed. As one skilled in the art knows and understands, various factors (eg, including free radical initiator, solids, weight ratio S: AN, process conditions, etc.) affect the optimal amount of preformed stabilizer. .

  Also, polyurethanes (preferably polyurethane foams) comprising polymer polyols and methods for their production are part of the present invention. Suitable polymer polyols for these polyurethanes can be either made directly from ethylenically unsaturated macromers or made from preformed stabilizers based on ethylenically unsaturated macromers. These polyurethanes comprise the reaction product of a polyisocyanate component or a prepolymer thereof and an isocyanate-reactive component comprising the polymer polyol of the present invention. These methods for producing polyurethane include reacting a polyisocyanate component or a prepolymer thereof with an isocyanate-reactive component comprising the polymer polyol of the present invention.

  In addition to use as stabilizers in the production of polyether polymer polyols, the reactive unsaturation containing stabilizers of the present invention are also useful for other products (eg, but not limited to, impact modifiers). Can be used. For example, a preformed vinyl polymer impact modifier includes a reactive unsaturation containing stabilizer, one or more polymerizable vinyl monomers (eg, those discussed above), and a plurality of unsaturated monomers (eg, butadiene). Etc.) can be reacted. The polymerization can be positively affected in solution in a suitable solvent or in a normal or reverse emulsion in an aqueous system. Reactive unsaturation containing stabilizers can also be used as stabilizers for cement additives by copolymerization with monomers (eg, acrylic acid). Stabilizers can also serve as reactants in radiation curable coatings.

  As used herein, the phrase “polyol feed” refers to the amount of base polyol feed present in a polymer polyol or present in a process for making a polymer polyol.

  As used herein, the phrase “total feed” is present in each of various products (ie, preformed stabilizers, polymer polyols, etc.) and / or various products. Means the sum of all components present in each production method.

  As used herein, all numerical ranges, amounts, values and percentages in the following portions of the specification (eg, for material amounts, reaction times, unless otherwise indicated) And temperature, quantity ratio, molecular weight value, and others) as if the term “about” is preceded even if the term “about” is not expressly expressed with the value, amount or range. Can be read.

  The following examples illustrate details for the preparation and use of the compounds of this invention. The invention described as disclosed above is not limited in spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and methods of the following manufacturing procedures can be used to produce these compounds. Unless otherwise indicated, all temperatures are degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.

The following ingredients were used in the examples.
(Polyol A)
Glycerin starting polyether polyol prepared by reacting propylene oxide and ethylene oxide in the presence of potassium hydroxide catalyst and purifying to remove the catalyst. The resulting polyol has a hydroxyl number of about 52, a number average molecular weight of about 3235 and a functionality of about 3.
(Polyol B)
A sorbitol starting polyether polyol prepared by reacting propylene oxide and ethylene oxide in the presence of a potassium hydroxide catalyst and purifying to remove the catalyst. The resulting polyol has a hydroxyl number of about 28, a number average molecular weight of about 12,020 and a functionality of about 6.
(Polyol C)
Trimethylolpropane starting polyether polyol prepared by reacting propylene oxide and ethylene oxide in the presence of potassium hydroxide catalyst and purifying to remove the catalyst. The resulting polyol has a hydroxyl number of about 28, a number average molecular weight of about 6,000 and a functionality of about 3.

(Isocyanate A)
Diphenylmethane 4,4′-diisocyanate (MDI), commercially available from Bayer Polymers.
(Catalyst A)
Polyurethane amine catalyst suitable for foam, sold as NIAX Catalyst A-1 from Dow Chemical Company.
(Catalyst B)
A polyurethane foam catalyst comprising stabilized stannous octoate, commercially available as T-9 from Air Products.
(Surfactant A)
Silicone surfactant suitable for use in foam, commercially available as “Silicone Surfactant L-620” from Dow Chemical Company.
(BHT)
Butylated hydroxytoluene (TDI)
Mixture of 80% by weight of 2,4-diisocyanatotoluene and 20% by weight of 2,6-diisocyanatotoluene (initiator A)
tert-Butyl peroxide (TBPO)
(Initiator B)
Azobis (isobutyronitrile), commercially available as VAZO 64 from DuPont.

The following properties and units are used in the examples in addition to the properties and units of ASTM.
(viscosity)
Viscosity was measured using a Cannon-Fenske viscometer.
(density)
Density (lb / ft ³ ) (ASTM D-3574, Test A)
(IFD 25%)
Indentation Force Deflection 25% (ASTM D-3574, Test B1 and Test B2)
(IFD65%)
Deflection force 65% (ASTM D-3574, Test B1 and Test B2)
(IFD65 / 25)
65% deflection due to dent force divided by 25% deflection due to dent force (ASTM D-3574, Test B1 and Test B2)
(tension)
Tensile strength (psi) (ASTM D-3574, Test E)
(Elongation)
Elongation (%) (ASTM D-3574, Test E)
(Tear)
Tear resistance (pound / inch) (ASTM D-3574, Test F)

[General procedure for Macromer]
(Macromer I)
Macromer I was prepared by reacting acrylic acid (1 mol) with polyol C (1 mol) via azeotropic esterification using 0.1 wt% p-toluenesulfonic acid and toluene as solvent. .
(Macromer II)
Polyol B was charged to a stirred reactor and heated to 80 ° C. The reactor was then charged with maleic anhydride (0.889 wt% based on polyol B loading). After thorough mixing of the polyol and maleic anhydride mixture, 60 ppm of KOH was added and the mixture was allowed to react at 110 ° C. for 1 hour. The acid groups were then capped with ethylene oxide (1.0 wt% based on polyol B loading) by stirring the mixture at 110 ° C. until the acid value was reduced to <0.4 mg KOH / g. The mixture was then vacuum stripped to remove residual EO and reacted with morpholine (1000 ppm) at 80 ° C. for 6 hours. The molar ratio of maleic anhydride to polyol was 0.55.
The mixture described in the above paragraph was charged with isocyanate A (0.93% by weight based on polyol B loading). The mixture was reacted at 63 ° C. to reach a viscosity of 6500 cSt and inhibited with BHT (500 ppm). This product is referred to herein as Macromer II.

(Macromer III)
Methyl acrylate (0.35 mol) was reacted with polyol B (0.58 mol) at 205 ° C. in the presence of a titanium butoxide catalyst (200 ppm). A fractionation column was used to hold the acrylate in the flask as methanol was distilled off. The measured molar ratio was 0.40 mole acrylate / 1 mole polyol. This product is referred to herein as Macromer III.
(Macromer IV)
Using the method described above for Macromer III, Macromer IV was prepared using methyl methacrylate instead of methyl acrylate. The measured molar ratio was 0.40 mole methacrylate / 1 mole polyol.
(Macromer V)
Macromer V was prepared by reacting methacrylic acid (1 mol) and polyol B (1 mol) via azeotropic esterification using 0.1 wt% p-toluenesulfonic acid and toluene as solvent. . The measured molar ratio was 0.45 mole methacrylate / 1 mole polyol.

[Preformed stabilizer (PFS) formulation]
This series of examples relates to the preparation of preformed stabilizers prepared from macromers I to V, respectively, to obtain PFS I to V. Each preformed stabilizer is mixed in a two-stage reaction system comprising a continuous stirred tank reactor (CSTR) (first stage) and a plug flow reactor (second stage) equipped with an impeller and four baffles. Manufactured. The residence time in each reactor was about 60 minutes. The reactants were continuously pumped from the feed tank through the in-line static mixer and then through the feed tube into the reactor. This was mixed well. The temperature of the reaction mixture was controlled at 120 ± 1 ° C. The product from the second stage reactor was continuously overflowed through a pressure regulator intended to control the pressure in each stage to 65 psig. The preformed stabilizer was then sent through a condenser into the collection vessel. The formulations used for the preformed stabilizer are listed in Table 1.

[ Reference Examples 1 and 2, Examples 3 to 5 ]
This series of examples and reference examples relate to the production of polymer polyols, each prepared from preformed stabilizers I-V. Each polymer polyol was prepared in a two-stage reaction system comprising a continuous stirred tank reactor (CSTR) (first stage) and a plug flow reactor (second stage) equipped with an impeller and four baffles. The residence time in each reactor was about 60 minutes. The reactants were continuously pumped from the feed tank through the in-line static mixer and then through the feed tube into the reactor. This was mixed well. The temperature of the reaction mixture was controlled at 115 ± 1 ° C. The product from the second stage reactor was continuously overflowed through a pressure regulator intended to control the pressure in each stage to 45 psig. The polymer polyol was then sent through a condenser and into a collection vessel. The crude product was vacuum stripped to remove volatiles. The weight percent of total polymer in the product was calculated from the monomer concentration measured in the crude polymer polyol before stripping. The parameters used in the experiment are listed in Table 2.

[Examples 6 and 7]
These examples relate to the production of free rise foams from commercially available polymer polyols and the polymer polyols prepared in Example 4.
The polymer polyol, amine catalyst, and silicone surfactant were added to a 1/2 gallon cylindrical paper container equipped with a baffle. The contents were mixed for 60 seconds at 2400 rpm using a stirrer with two turbine impellers. The mixture was then degassed for 10 seconds. After degassing, tin catalyst was added and the contents were mixed at 2400 rpm for 10 seconds. While rotating the mixer, toluene diisocyanate was added and the contents were mixed for 5 seconds. The mixture was then poured into a 14 × 14 × 6 inch cardboard box. Here it swelled freely until the reaction was complete. The foam was then heated in an oven at 225 ° C. for 5 minutes. Foam properties were determined according to ASTM standard standard D-3574-66. The parameters used in the experiment are listed in Table 3.

  Although the present invention has been described in detail above for purposes of illustration, such details are solely for the purpose of the invention, and the spirit of the invention, except as may be limited by the claims. It should be understood that variations can be made by those skilled in the art without departing from the scope and scope.

Embodiments of the present invention include the following.
[1] Formula (a):

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
And A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) an ethylenically unsaturated macromer comprising the product reacted in the presence of at least one catalyst.
[2] In compound (a),
R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
R ″ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an ethenyl group or a propenyl group;
And A represents a chlorine atom, a bromine atom, an iodine atom, or an OR ′ group (wherein R ′ represents hydrogen, a methyl group, or an ethyl group), Macromer.
[3] (b) The ethylene of claim 1, wherein the polyether polyol has a functionality of about 3 to about 10, an OH number of about 15 to about 200, and a molecular weight of about 2,000 to about 12,000. Unsaturated macromer.
[4] (a) The ethylenically unsaturated macromer according to the above item 1, comprising methyl methacrylate.
[5] (1) Formula (a):

[Where,
R represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1 to 8 carbon atoms, or an aryl group containing 6 to 12 carbon atoms;
R ″ represents a hydrogen atom, a branched or straight chain hydrocarbon group containing 1-8 carbon atoms, which may be saturated or unsaturated, or an aryl group containing 6-12 carbon atoms. Show
And A represents a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 2 to 15,
If necessary,
(C) A process for producing an ethylenically unsaturated macromer comprising reacting in the presence of at least one catalyst.

[6] In compound (a),
R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
R ″ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an ethenyl group or a propenyl group;
And A represents a chlorine atom, a bromine atom, an iodine atom, or an OR ′ group (wherein, R ′ represents a hydrogen atom, a methyl group, or an ethyl group).
[7] The method of claim 5, wherein the polyether polyol has a functionality of about 3 to about 10, an OH number of about 15 to about 200, and a molecular weight of about 2,000 to about 12,000. .
[8] The method according to item 5 above, wherein (a) comprises methyl methacrylate.
[9] The method according to item 5 above, wherein the reaction between (a) and (b) is a reaction for about 1 hour to about 10 hours at a temperature of about 25 ° C. to about 250 ° C. .
[10] (A) The ethylenically unsaturated macromer according to item 1 above,
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
And (E) a preformed stabilizer comprising a product subjected to free radical polymerization in the presence of a chain transfer agent as required.

[11] (A) The ethylenically unsaturated macromer is
(A) Formula:

[Where,
R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
R ″ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an ethenyl group, or a propenyl group;
And A represents a chlorine atom, a bromine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom, a methyl group or an ethyl group). ]
A compound corresponding to
(B) A reaction product of a polyether polyol having a functionality of about 3 to about 10, an OH number of about 15 to about 200, and a molecular weight of about 2,000 to about 12,000. Preformed stabilizer.
[12] (B) The preformed stabilizer according to the above item 10, wherein the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and a mixture thereof.
[13] The preformed stabilizer according to the above item 12, wherein (B) comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 40:60.
[14] (C) The preformed stabilizer according to item 10, wherein the free radical initiator is selected from the group consisting of one or more peroxide initiators, one or more azo initiators, and mixtures thereof. .
[15] (D) The preformed stabilizer according to item 10, wherein the diluent is selected from the group consisting of monools, polyols, hydrocarbons, ethers and mixtures thereof.

[16] (E) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, and methylene chloride. 11. The preformed stabilizer of claim 10 selected.
[17] (1) (A) The ethylenically unsaturated macromer according to item 1 above,
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
And (E) A method for producing a preformed stabilizer, which includes free radical polymerization in the presence of a chain transfer agent as required.
[18] (A) The ethylenically unsaturated macromer is
(A) Formula:

[Where,
R represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group;
R ″ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, an ethenyl group, or a propenyl group;
And A represents a chlorine atom, a bromine atom, an iodine atom, or an OR ′ group (wherein R ′ represents a hydrogen atom, a methyl group or an ethyl group). ]
A compound corresponding to
(B) A reaction product of a polyether polyol having a functionality of about 3 to about 10, an OH number of about 15 to about 200, and a molecular weight of about 2,000 to about 12,000. the method of.
[19] The method according to Item 17, wherein (B) the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and a mixture thereof.
[20] The method according to item 19, wherein (B) comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 40:60.

[21] The method of paragraph 17, wherein the free radical initiator is selected from the group consisting of one or more peroxide initiators, one or more azo initiators, and mixtures thereof.
[22] (D) The method according to the above item 17, wherein the diluent is selected from the group consisting of monools, polyols, hydrocarbons, ethers and mixtures thereof.
[23] (E) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform, and methylene chloride. The method of claim 17, wherein the method is selected.
[24] (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the preformed stabilizer according to item 10 above,
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A polymer polyol comprising the reacted product.
[25] (III) The polymer polyol according to item 24, wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, acrylonitrile and mixtures thereof.

[26] (III) The polymer polyol according to the above item 25, wherein the ethylenically unsaturated monomer comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 30:70.
[27] (IV) The polymer polyol according to item 24, wherein the free radical polymerization initiator is selected from the group consisting of acyl peroxides, alkyl peroxides, azo compounds, and mixtures thereof.
[28] (V) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform and methylene chloride. 25. The polymer polyol according to item 24, wherein
[29] (1) (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the preformed stabilizer according to item 10 above,
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A method for producing a polymer polyol, comprising free radical polymerization.
[30] (III) The method according to item 29, wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, acrylonitrile and mixtures thereof.

[31] (III) The method according to item 30, wherein the ethylenically unsaturated monomer comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 30:70.
[32] (IV) The method according to item 29, wherein the free radical polymerization initiator is selected from the group consisting of acyl peroxides, alkyl peroxides, azo compounds, and mixtures thereof.
[33] (V) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform and methylene chloride. 30. The method of paragraph 29 above.
[34] (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the ethylenically unsaturated macromer described in item 1 above;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A polymer polyol comprising the reacted product.
[35] (III) The polymer polyol according to the above item 34, wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, acrylonitrile and a mixture thereof.

[36] (III) The polymer polyol according to the above item 35, wherein the ethylenically unsaturated monomer comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 30:70.
[37] (IV) The polymer polyol according to the above item 34, wherein the free radical polymerization initiator is selected from the group consisting of acyl peroxides, alkyl peroxides, azo compounds and mixtures thereof.
[38] (V) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform and methylene chloride. 35. The polymer polyol of claim 34, wherein
[39] (1) (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the ethylenically unsaturated macromer described in item 1 above;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A method for producing a polymer polyol, comprising free radical polymerization.
[40] (III) The method according to Item 39, wherein the ethylenically unsaturated monomer is selected from the group consisting of styrene, acrylonitrile and mixtures thereof.

[41] (III) The method according to the above item 40, wherein the ethylenically unsaturated monomer comprises a mixture of styrene and acrylonitrile in a weight ratio of 80:20 to 30:70.
[42] The method according to Item 39, wherein the free radical polymerization initiator is selected from the group consisting of acyl peroxides, alkyl peroxides, azo compounds, and mixtures thereof.
[43] (V) The chain transfer agent is selected from the group consisting of isopropanol, ethanol, tert-butanol, toluene, ethylbenzene, triethylamine, dodecyl mercaptan, octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, chloroform and methylene chloride. 40. The method of paragraph 39 above.
[44] A method for producing polyurethane, comprising reacting (1) polyisocyanate with (2) an isocyanate-reactive component comprising the polymer polyol according to item 24.
[45] A method for producing polyurethane, comprising reacting (1) polyisocyanate with (2) an isocyanate-reactive component comprising the polymer polyol according to item 34 above.

Claims (9)

(A) Formula:

[Where,
R represents a hydrogen atom or a methyl group ;
R ″ represents a hydrogen atom or a methyl group ,
And A represents an OR 2 group (wherein R ′ represents a hydrogen atom or a methyl group ). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 4 to 15;
If necessary,
(C) an ethylenically unsaturated macromer comprising a product reacted in the presence of at least one catalyst , wherein components (a) to (c) are components (a ) And the component (b) are reacted so that the molar ratio of the component (a) is 0.40 mol to 0.45 mol / component (b) 1 mol . (1) (a) Formula:

[Where,
R represents a hydrogen atom or a methyl group ;
R ″ represents a hydrogen atom or a methyl group ,
And A represents an OR 2 group (wherein R ′ represents a hydrogen atom or a methyl group ). ]
A compound corresponding to
(B) a polyether polyol having an OH number of 10 to 300 and a functionality of 4 to 15;
If necessary,
(C) A process for producing an ethylenically unsaturated macromer comprising reacting in the presence of at least one catalyst , wherein components (a) to (c) The method of making it react so that the molar ratio of a) and a component (b) may become the range of the component (a) 0.40 mol-0.45 mol / component (b) 1 mol . (A) the ethylenically unsaturated macromer according to claim 1;
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
And (E) a preformed stabilizer comprising a product subjected to free radical polymerization in the presence of a chain transfer agent as required. (1) (A) the ethylenically unsaturated macromer according to claim 1;
(B) at least one ethylenically unsaturated monomer;
(C) at least one free radical polymerization initiator,
And (D) a liquid diluent as required,
And (E) A method for producing a preformed stabilizer, which includes free radical polymerization in the presence of a chain transfer agent as required. (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the preformed stabilizer of claim 3;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A polymer polyol comprising the reacted product. (1) (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the preformed stabilizer of claim 3;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A method for producing a polymer polyol, comprising free radical polymerization. (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the ethylenically unsaturated macromer of claim 1;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A polymer polyol comprising the reacted product. (1) (I) a base polyol having an OH number of 10 to 180 and a functionality of 2 to 8,
(II) the ethylenically unsaturated macromer of claim 1;
(III) at least one ethylenically unsaturated monomer,
(IV) at least one free radical polymerization initiator,
And optionally (V) in the presence of a chain transfer agent,
A method for producing a polymer polyol, comprising free radical polymerization.   (1) A process for producing a polyurethane comprising reacting a polyisocyanate with (2) an isocyanate-reactive component comprising the polymer polyol according to claim 5.